[Pd(η2-fumaronitrile)(N-(2-(diphenylphosphino)benzylidene)(isopropyl)amine)] | 635702-11-3

• 英文名称: [Pd(η2-fumaronitrile)(N-(2-(diphenylphosphino)benzylidene)(isopropyl)amine)]
• 英文别名: (η2-fumaronitrile)(Ph2PC6H4CHNiPr)palladium(0)
• CAS: 635702-11-3
• 化学式: C₂₆H₂₄N₃PPd
• 分子量: 515.89
• InChiKey: YCUWTRVOZHVZDG-RBHSZMTFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  (allyl)[2-(diphenylphosphino)-N-(1-methylethyl)benzylideneamine]palladium tetrafluoroborate 、 反丁烯二腈 在 二乙胺 作用下， 以 not given 为溶剂， 以93%的产率得到[Pd(η2-fumaronitrile)(N-(2-(diphenylphosphino)benzylidene)(isopropyl)amine)]
  参考文献：
  名称：

  Mechanistic study on the cross-coupling of alkynyl stannanes with aryl iodides catalyzed by η²-(dimethyl fumarate)palladium(0) complexes with iminophosphine ligands

  摘要：

  在伪一阶条件下研究了[Pd(δ-2-dmfu)(PâN)][dmfu = 富马酸二甲酯；PâN = 2-(PPh2)C6H4-1-CHNR, R = C6H4OMe-4 (1a), CHMe2 (2a)] 和[Pd(δ-2-dmfu)(PâN)2]与 IC6H4CF3-4、ISnBu3 和 PhCCSnBu3 的反应。IC6H4CF3-4 的氧化加成反应生成了[PdI(C6H4CF3-4)(PâN)]（1b 或 2b）。与 PhCCSnBu3 不发生反应，与 ISnBu3 在过量 PhCCSnBu3 的存在下也不发生反应。在富马腈（fn）存在的情况下，1b 和 2b 通过 PhCCSnBu3 发生反金属反应，然后快速还原消除，生成 [Pd(δ-2-fn)(PâN)]。同样的反应顺序也发生在[PdI(C6H4CF3-4)(PâN)]/PâN（1ⶠ1 摩尔比）体系中，生成[Pd(δ-2-fn)(PâN)2]。钯（0）配合物是 PhCCSnBu3 与芳基碘化物 ArI（Ar = C6H4CF3-4，Ph）发生交叉偶联反应的活性催化剂。催化效率取决于配合物：[Pd(δ-2-dmfu)(PâN)2] > [Pd(δ-2-dmfu)(PâN)]，以及取代基 R：C6H4OMe-4 > CHMe2。反应活性和光谱数据表明，催化循环涉及 ArI 与钯(0)物种的初始氧化加成，然后是产物的反金属化和快速还原消除以再生起始钯(0)化合物。对于作为催化剂的[Pd(δ-2-dmfu)(PâN)]来说，氧化加成是决定速率的步骤，而对于[Pd(δ-2-dmfu)(PâN)2]来说，氧化加成和脱金属步骤的速率相当。

  DOI：

  10.1039/b300020f

文献信息

• Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η ² ‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes
  作者：Bruno Crociani、Simonetta Antonaroli、Luciano Canovese、Paolo Uguagliati、Fabiano Visentin

  DOI：10.1002/ejic.200300376

  日期：2004.2

  dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3-4) to 1a and 2a lead to the products [PdI(Ar)(P-N)] (1c, 2c) and obey the rate law, k(obs) = k(1A) + k(2A)[ArI]. The k(1A) step involves oxidative addition to a reactive species [Pd(solvent)(P-N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(eta(2) -dmfu)

  配合物 [Pd(eta(2)-dmfu)(PN)] dmfu = 富马酸二甲酯；PN = 2-(PPh2)C6H4-1-CH=NR, R = OMe-4 (1a), CHMe2 (2a), Me2-2,6 (3a), C6H3(CHMe2)(2)-2,6 ( 4a)} 在溶液中经历动态过程，包括 PN 配体位点交换，通过 Pd-N 键在较低能量下的初始断裂和在较高能量下的烯烃离解-缔合。根据烯烃置换的平衡常数值，复合物 [Pd(eta(2)-fn)(PN)]（fn = 富马腈，1b）比其 dmfu 类似物 1a 具有更高的热力学稳定性。ArI (Ar = CF3-4) 氧化加成到 1a 和 2a 的动力学导致产物 [PdI(Ar)(PN)] (1c, 2c) 并遵守速率定律，k(obs) = k( 1A) + k(2A)[ArI]。k(1A) 步骤涉及对由 dmfu
• Kinetics and mechanism of regioselective amination of the 1-phenylallyl group in cationic palladium(II) complexes bearing bidentate ligands
  作者：Bruno Crociani、Simonetta Antonaroli、Luciano Canovese、Fabiano Visentin、Paolo Uguagliati

  DOI：10.1016/s0020-1693(01)00333-4

  日期：2001.4

  The complexes [Pd(eta (3)-1-PhC3H4)(L-L')(=) [L-L' = 2-(PPh2)C6H4-1-CH=N (R = Me (1a), i-Pr (1b), t-Bu (1c), (R)-bornyl (1d), C6H4OMe-4 (1e), C6H3Me2-2,6 (1f), C6H3(i-Pr)(2)-2,6 (1g)), 6-MeC5H3N-2-CH=NC6H4OMe-4 (2a), C5H4N-2-CH=N-t-Bu (2b) and C5H4N-2-CH2S-t-Bu (3a)] are generally present in solution as two geometrical isomers, the relative abundance of which depends essentially on the steric requirements of the L-L' ligand. In the presence of fumaronitrile the cationic complexes undergo a regioselective amination by secondary amines HY at the CH, allyl terminus, yielding [Pd(eta (2)-fn)(L-L')] and the allylamines (E)-PhCH=CHCH2Y. Under pseudo-first-order conditions the amination rates (k(obs)) are found to depend on the k(2)[HY] term for 2a and 3a, and on the sum k(2)[HY] + k(3)[HY](2) for the other complexes. The second-order term k(2) is related to direct nucleophilic attack on the CH, allyl terminus of the substrate whereas the third-order term k(3) is ascribed to parallel attack by a further HY molecule on the intermediate [Pd(1-PhC3H4)(L-L')(HY)](+). The k(2) values depend on the steric and electronic properties of both the amine HY and the ligand L-L'. For complexes 1a-1g, the relatively higher k(2) values and their increase with increasing steric crowding at the nitrogen-bonded carbon of substituent R are interpreted in terms of a greater reactivity of the isomer with the CH2 allyl terminus trans to phosphorus and cis to the NR group. The high amination rate of 2a, as compared with that of 2b, is related to substantial steric interaction of the CH2 allyl terminus with the 6-Me pyridine group in close proximity in the predominant isomer. (C) 2001 Elsevier Science B.V. All rights reserved.